Simultaneous copolymerization and alkylation of heterocyclic n-vinyl monomers with alpha-olefins



United States Patent Ofiice Patented Jan. 21, 1969 3,423,381SIMULTANEOUS COPOLYMERIZATION AND ALKYLATION F HETEROCYCLIC N-VINY LMONOMERS WITH a-OLEFINS Ashot Merijan, Clark, and Frederick Grosser,Midland Park, N.J., assignors to GAF Corporation, New York, N.Y., acorporation of Delaware No Drawing. Continuation-in-part of applicationScr.

No. 358,406, Apr. 8, 1964. This application Nov. 18, 1965, Ser. No.508,546

U.S. Cl. 260--88.1

Int. Cl. C08? 7/12; A61lt 7/00; Clllm 3/26 This application is acontinuation-in-part of our application Ser. No. 358,406, filed on Apr.8, 1964, now abandoned.

This invention relates to a new process of simultaneously copolymerizingand alkylating heterocyclic N-vinyl monomers with tx-olefins to yield arange of copolymers having solubility characteristics in a wide range ofsolvents, from polar to non-polar, and to the new and useful class ofsuch alkylated copolymers.

It is known that homopolymers of N-vinyl lactams are soluble in waterand in a certain class of organic solvents such as alcohols,ether-alcohols, amines, and other polar organic solvents, but insolublein aliphatic hydrocarbons such as hexane, heptane, cyclohexane,methylcyclohexane, mineral spirits, mineral oil, lubricating oil, andother 22 Claims non-polar organic solvents.

Commercial requirements have arisen for homopoly mers and copolymers ofN-vinyl lactams which possess the characteristics imparted by thepresence of the lactam rings, but which have special solubilitycharacteristics that are dictated by the particular end use in view. Forexample, polyvinylpyrrolidone, and copolymers oi vinylpyrrolidone andvinyl acetate, are very effective as hair-grooming aids, but for certainapplications their solubility in water is undesirable. Hence, suchpolymers with a lower degree of hygroscopicity and an increased moistureresistance are special requirements that have been dictated by thecosmetic trade. In another instance the effectiveness ofpolyvinylpyrrolidone and copolymers thereof as dispersing agents inlubricating oils cannot be utilized because of their insolubility in thelubricating medium. In still another instance, the excellent adhesiveproperties imparted to the polymer by the lactam ring are partlyvitiated because of poor moisture resistance. A further example is theinability to utilize the excellent complexing ability ofpolyvinylpyrrolidone as a disperse dye receptor in difiicult-to-dyeresins such as polyethylene and polypropylene because of theinsolubility of polyvinylpyrrolidone in such resins.

It is also known that polymers of N-vinyl lactams in which the regularlyrecurring lactam rings are substituted by one or more lower alkyl groupscan be prepared by conventional polymerization procedures of lower alkylsubstituted N-vinyl lactams. Monomers of the latter type, such asN-vinyl-3-butyl pyrrolidone, N-vinyl-S-methyl- 5-ethyl pyrrolid'one,N-vinyl-3,3,5-trimethyl pyyrolidone, N-vinyl-6-butyl piperidone,N-viny1-7-ethyl caprolactam, N-vinyl 3,5 dimethyl caprolactam,N-vinyl-4-isopropyl caprolactam, N-vinyl-3,5,7-trimethyl caprolactam,etc., when homopolymerized, yield water soluble polymers with additionalsolubility in lower alcohols, nitroethane, butylamine, etc., butinsoluble in hexane, kerosene, mineral oils and other aliphatic andaromatic hydrocarbons. In view of these solubility characteristics, suchpolymers have limited applications. For example, such polymers cannot beused in applications where waterproofness is a prime requisite. Theycannot be used as thickeners in mineral oils or as gloss improvers ofwaxes and polishes. They are incompatible with Waxes and cannot beemployed as emollients in cosmetics and soaps.

Copolymers of N vinyl lactams and methyl acrylate, acrylic acid, vinyllaurate, etc, are also soluble in alcohols, and to varying degrees inwater, depending on the character and the amount of the comonomercontained in the copolymer. Solubility in water decreases as thenon-polar nature of the co-monomer increases and as the percentage ofcomonomer in the copolymer increases. Such as copolymers are, however,insoluble or partially soluble in the aforementioned aliphatichydrocarbons.

It is the principal object of the present invention to provide a newclass of alkylated copolymers of heterocyclic N-vinyl monomers anda-olefins which have varying degrees of solubility in polar andnon-polar solvents and which will meet the uses dictated 'by commercialrequirements.

A further object is to provide a new process of simultaneouslycopolymerizing and alkylating heterocyclic N-vinyl monomers witha-olefins so as to systematically control the solubility of thealkylated copolymers. Thus, by the proper choice of copolymerizing andalkylating agent (ll'OlCfiI'l) and the degree of copolymerization andalkylation, copolymers are obtained which are soluble in polar solvents,such as alcohols, but which are much less sensitive to moisture, orcopolymers which are soluble in aliphatic hydrocarbons of from 6 to 60carbon atoms including isomers thereof, mineral and lubricating oilshaving a Saybolt viscosity of from 50 to 200 seconds, or copolymershaving intermediate degrees of solubility t between polar and non-polarsolvents. This systematic control of the solubility characteristics ofthe alkylated copolymer is achieved without destroying the otherdesirable characteristics imparted by the heterocyclic ring, and thusalkylated copolymers can be prepared which overcome the deficienciesdescribed above.

Other objects and advantages will become manifest from the followingdescription:

We have found that heterocyclic N-vinyl monomers are readilycopolymerized and alkylated with an a-olefin by treating one mole ofsuch monomer with 0.05 to 10 moles of an a-olefin of at least 2 carbonatoms in solution of an organic solvent common to the monomer and thea-olefin in the presence of 0.025 to 0.30 mole of an organic peroxidecatalyst per mole of a-olefin at a temperature ranging from to 200 C.for a period of time ranging from 3 to 60 hours. The resulting solutionof copolymerized and alkylated copolymer may be employed as such or, ifdesired, the organic solvent may be removed by vacuum distillation. Thesolubility of the resulting copolymer in polar solvents decreases andthe solubility in non-polar solvents increases as the molar ratio oftit-olefin to heterocyclic N-viny l monomer increases. In other words,alkylated copolymers are obtained in which some or all of theheterocyclic N-vinyl moieties contain one or more alkyl groups of fromat least 2 carbon atoms to as many carbon atoms as is contained in thea-olefin employed in the reaction.

The heterocyclic N'vinyl monomers which are simultaneously copolymerizedand alkylated with an a-olefin of at least 2 carbon atoms in accordancewith the present invention are characterized by the following formula:

wherein R and R are selected from the group consisting of hydrogen,methyl, and ethyl, and n is an integer of from 1 to 3. Such monomersinclude N-vinyl pyrrolidone, N-vinyl-S-methyl pyrrolidone,N-vinyl-Sethyl pyrrolidone, N-vinyl-5,5 dimethyl pyrrolidone,N-vinyl-S,5-diethyl pyrrolidone and N-vinyl-S-methyl-S-ethylpyrrolidone; N-vinyl piperidone, N-vinyl-6'methyl piperidone, N- vinyl 6ethyl piperidone, N-vinyl-6,6-dimethyl piperidone, N-vinyl-6,6-diethylpiperidone and N-vinyl-6- methyl-6-ethyl piperidone; N-vinylcaprolactam, N-vinyl- 7-methyl caprolactam, N-vinyl-7,7-dimethylcaprolactam, N-vinyl-7-ethyl caprolactam, N-viny1-7,7-diethy1caprolactam and N-vinyl-7-methyl-7-ethyl caprolactam, as described inUnited States Patents 2,265,450; 2,317,804; 2,335,454 and many otherstoo numerous to mention in which working examples of some of the speciescharacterized by the above formula are given.

Another group of heterocyclic N-vinyl monomers comprises comparablemonomers of the corresponding N- viny1 6- and 7-membered thiolactams,i.e., wherein oxygen of the carbonyl function in the foregoing formulais replaced by sulfur; N-vinyl succinimide, N-vinyl diglycolylirnide,N-vinyl glutarimide, N-vinyl-3-morpholinone,N-vinyl-S-methyl-3morpholinone, N-vinyl-S-ethyl- 3-morpholinone, andN-vinyl oxazolidone.

Still another group of N-heterocyclic monomers includes polymerizablemonomers obtained by the reaction of 5-, 6- and 7-membered lactams withacryloyl or methacryloyl chloride or bromide in the presence of ahydrogen halide acceptor such as pyridine, dimethylaniline, etc., havingthe structure:

wherein R, R and n have the same values as above, and R is eitherhydrogen or methyl. Illustrative compounds areN-methacryloyl-pyrrolidone, -piperidone and caprolactam;N-methacryloyl-S-methylpyrrolidone, N-methacryloyl-6-methylpiperidoneand N-methacryloyl-7-methyl caprolactam', N-acryloyl-pyrrolidone,-piperidone and -caprolactam; N-acryloyl-S-methylpyrrolidone,N-acryloyl-6-methylpiperidone and N-acryloyl-7-methyl caprolactam;compounds having the structure:

wherein R, R and n have the same values as above, R is either hydrogenor methyl, R represents hydrogen, an alkyl of from 1 to 4 carbon atomsor phenyl group and y represents an integer of from 1 to 3. Illustrativecomcounds of this type are N-methacrylamidomethyl-, N-methacrylamidoethyl-, N-methacrylamidopropyland N- (Nphenylaerylamidopropyl)-pyrrolidones, -piperidones and -caprolactams,which are readily prepared by reacting acryloyl or methacryloyl chlorideor bromide with an N-(aminoalkyl)-lactam in the presence of anyconventional base to take up the hydrogen halide.

It is to be understood that the nature or character of theN-heterocyclic polymerizable monomer that may be used in the process ofthe present invention is immaterial so long as it contains a carbonylfunction in the ring adjacent to the nitrogen atom thereof and at leastone active proton in its monomer moiety. Such monomer will copolymerizewith an ot-olefin or halo'a-olefin and alkylate with the said a-olefinas will be pointed out hereinafter.

Any a-olefin having a molecular weight from about 28 to as high as 2500may be employed as the co-monomer and in the alkylation of the activesites in the moieties of the N-heterocyclic monomer during thesimultaneous copolymerization and alkylation reaction, In other words,a-olefins ranging from ethene (ethylene) to as high as polybuteneshaving molecular weights from 400 to 2500 may be employed. As examplesof such a-olefins the following are illustrative: ethene; propene;l-butene; l-pentene; 2-ethyll-butene; Z-methyl-l-pentene; 1-hexene; 5-methyl-l-hexene; 2-methyl-1-pentene; l-hexene; S-methyll-hexene;Z'methyI-I-pentene; 3-ethyl-1-pentene; l-heptene; l-octene; l-nonene;2-ethyl-l-hexene; l-decene; 1 dodecene; l-tetradecene; l-hexadecene;l-heptadecene; l-octadecene; l-nonadecene; l-eicosene; l-docosene; 1-tetracosene; l-pentacosene; trimerized a-tetradecene and polybutenes ofmolecular weight of 400 to 2500 may be used.

While linear ot-olefins are preferred because of their commercialavailability, numerous isomers of a-olefins ranging from l-pentene tol-pentacosene as well as polybutenes may also be employed in thealkylation reaction. The only precaution required in such. case is thatthe isomer contain an ethylenic unsaturation in the wposition thereof.

A mixture of commercially available linear a-olefins produced bycracking petroleum wax or by polymerizing lower olefins may also be usedas the co-monomer and alkylating agent, Alpha-olefins in the carbonrange of from C9-Cn (H -C 5; and C15-C20 are commercially available andcontain from 81 to 87 weight percent of straight-chain a-olefins; from0.5 to 2 weight percent of straight-chain internal olefins; from 13 to 3weight percent of branched and naphthenic olefins; from 2 to 4 weightpercent of parafiins and naphthenes and from 1 to 1 of aromatics,respectively. A mixture of wolefins containing from 6575% of u-olefinsof from C to C and having an average molecular weight of 366 is alsocommercially available and such mixture is employed in the alkylationreaction.

Instead of employing ethylene (ethene) as the cornonomer and alkylatingagent, monohalo-u-olefins and polyhalo-a-olefins of at least 2 carbonatoms (hereinafter referred to simply as halo-a-olefins), such as, forexample, dichlorovinylidene fluoride (CCl CF chlorovinylidene fluoride(CI-ICl CF chlorotrifiuoroethylene (CCIF CF tetrafluoroethylene CF CFtetra chloroethylene ,(CCI CCl vinylidene fluoride (CHFCF vinylidenebromochloride, i.e., l-bromo-lchloroethylene (CH -CBrCl), vinylidenebroniofiuoride (CH CBrF), vinylidene chlorofluoride (CH CClF),1,2dichloro-1,2-difiuor0ethylene (CClF CClF), 1,2-difiuoroethylene (CHFCHF), 1-chloro-2-fiuoroethylene (CHF CHCI), 1-bromo-2-fiuoroethylene(Cl-IF CHBr) l-dichloro-Z-fiuoroethylene CHF CCl l-bromol ,2-difiuoroethylene (CHF CBrF), lhibromo-Z-fluoroethylene (CHF-" CBrQ,trichloroethylene (cliCl CCllchloro-1,2-dibromoethylene (CHBF CBrCl),trifiuoroethylene (CF CHF), tribromoethylene (CHBF CBl-bromo-Z-difluoroethylene (CF- CHBI'),l-chloro-lbromo-Z-difiuoroethylene (CF CBrCl), l-dibromo-2-difiuoroethylene (CF -CBr l-dichloro-Z-difiuoroethylene (CF CCll-bromo-Z-fiuoroethylene (CHF CHBr) l-chloro-2-difiuoroethylene (CFCHCI), 1-dichloro-2- difluoroethylene (CF CCl chlorotrifluoroethylene(CF CCIF) bromotrifiuoroethylene (CF CBrF fiuorotrichloroethylene (CCICCIF), trichloroiodoethylene (CClFCClI), chlorodiiodoethylene (CHCl:CI

1,2-dichloro-1,2 diiodoethylene (CCII CCII), l-bromo- 2-iodoethylene(CHI CHBr), l-iodo-2-chloroethylene (CHCI CHI), allyl chloride (CH CHCHCI), 4- chloro-l-butene (CH CHCH -CH Cl), 3,3,4,4,4-pentafiuoro-l-butene (CH CH-CF -CF 5-chloro l-pentene (CH =CHCH -CH CHCl), 3,3,4,4,5,5, S-heptafluoro-l-pentene (CH CHCF CF CF 3,3,4,4,5,5,6,6,6-nonafluoro-l-hexene is common to the alpha-olefin,halo-wolefin and the heterocyclic N-vinyl monomer. As solvents, variousalcof hols, such as methanol, ethanol, propanol, isopropanol,

butanol, sec-butanol, amyl alcohol, hexanol, 2-ethyl-lhexanol, ethyleneglycol, 1,2-butanediol, 4-butanediol, etc., may be employed. Othersolvents such as diethylene glycol, ethylene glycol monomethyl ether andthe like may also be employed. It is to be noted that the nature orcharacter of the organic solvent is immaterial so long as it forms asolution with the heterocyclic N-vinyl monomer, alpha-olefin(s), andhalo-m-olefin(s), and is relatively inert toward alkylation.

The amount of inert organic solvent employed is not critical. Any amountwhich will yield a solution of the heterocyclic N-vinyl monomer andalpha-olefin or haloa-olefin will suffice. However, for purposes ofexpediency,

3 we found that for every part by weight of heterocyclic N-vinylmonomer, from two to ten parts or organic solvent, either by volume orby weight, are sufiicient to yield a workable solution.

As peroxide catalysts (initiator) for the polymerization and alkylationreaction, any one of the known tertiary-alkyl organic peroxides andhydroperoxides such as, for example, di-Fbutyl peroxide, t-butylperbenzoate, dit-butyl perphthalate, t-butyl-pentamethyl-ethyl peroxide,t-butyl-triphenylmethyl peroxide, di-t-amyl peroxide, bis-(triethylmethyl) peroxide, bis-(triphenylmethyl) peroxide,2,5-dimethyl-hexyl-2,S-dihydroperoxide, 2,5-dimethyl- 2,5-di(t-butylperoxy) hexane, 2,5-dimethylhexyl-2,5-di (peroxy benzoate), t-butylhydroperoxide, para-menthane hydroperoxide and the like may be used.

Where it is desired that the alkylated copolymer be soluble in analiphatic liquid hydrocarbon of 6 or more carbon atoms, a mineral oil orlubricating oil of a paraffinic stock, the simultaneous copolymerizationand alkylation reaction is conducted in the presence of any one of theforegoing solvents. When the desired degree of copolymeriation andalkylation has been obtained, the reaction mixture is subjected tovacuum distillation and the removed solvent is replaced by a saturatedaliphatic hydrocarbon having a boiling point higher than the solvent.After the solvent has been removed there is ob tained a solution of thealkylated copolymer in solution of the aliphatic hydrocarbon. Saturatedaliphatic hydrocarbons having a boiling point higher than solvents arelegion and commercially available. Hence, no difficulty should beencountered in the selection of such hydrocarbon in preparing a solutionof the alkylated copolymer.

When low boiling ot-olefins of from 2 to 6 carbon atoms or low boilinglialo-a-olefins are employed in the reaction, in such case the organicperoxide catalyst, preferably di-t-butyl peroxide, and the solution ofthe heterocyclic N-vinyl monomer are added. into a stainless steelrocker bomb. The low-boiling tit-Olefin or hal0-u-olefin is then chargedto the bomb and the bomb heated and maintained at the same temperatureand period of time as noted above. The pressure developed in the bombmay range from 100 to 1000 p.s.i.g. After cooling the contents of thebomb to room temperature, they are discharged into any suitabledistillation equipment to remove the solvent and volatiles and theresidual product recovered either as a solid ranging from a waxy tocrystalline solid, or as a viscous liquid.

The percent of the wolefin or halo-a-olefin consumed in the simultaneouscopolymerization and alkylation re action ranges from 50% to 100% of thea-olefin charged. It is to be noted that in this reaction somehomopolymerization of the a-olefin takes place to the extent of 5percent of the wolefin consumed as determined by thermal gravimetricanalysis (TGA).

The degree of copolymerization and alkylation of the heterocyclicN-vinyl monomers with a-olefins and haloa-olefins, and the isomericdistribution of the alkyl groups in the moieties of such monomers, weredetermined by a systematic quantitative study of numerous alkylated c0-polymers prepared in accordance with the present invention and theirthermally degraded products by means of elemental analysis, vapor phasechromatography (VPC), infrared (IR) and nuclear magnetic resonance (NMR)spectroscopy. The data obtained from this extensive study showed severalgeneralizations from which the following equations were established:

The degree of copolymerization and alkylation based on the moles ofu-olefin (orhaloaz-olefin) charged in the reaction is determined by thefollowing equation:

(1) The mole percent of u-olefin copolymerized and alkylated=molepercent of a-olefin consumed The degree of copolymerization of thea-olefin charged is determined by the following equation:

(2) The minimum (a) and maximum (b) mole percent of the ct-olefincopolymerized:

Moles of hoterqzyclic N-vinyl monomer charged X 100 Moles of a-olefincharged Moles of heterocyelic N-vinyl monomer charged/l0 100 Moles ofa-olefin charged The mole percent of a-olefin that is consumed in thealkylation of the heterocyclic N-vinyl moieties is determined by thefollowing equation:

The mole percent of the heterocyclic N-vinyl moieties, that arealkylated on the average, is determined by the following equation: (4)The minimum(a) and the maximum (1)) mole percent of the heterocyclicN-vinyl moieties alkylated on the average:

Moles of (IE-Olefin chargedX II-JC :0 the result of Equation 3(a) X100 5Moles of N-vinyl monomer charged CIIC1 I- L z Moles of wolefin ehargedXq the result of Equation 3(1)) X100 1 Moles of N-vinyl monomer charged gEquations 2 to 4 inclusive, may be simplified as follows: 1 Y Min. molesof N-vmyl monomer charged/ 100 X100 (H2?),; CH2

moles of tit-olefin charged H Max moles of N vinyl monomer charged/ 10 X100 0 moles of a-olefin charged l OH I 2 20 t i (lnzresult of Equatlon 1r esult of Equation 2(1)) Mono-alkylation predominantly takes place whena high 0f Equatloll 1"reSu1t of Equation molar ratio of heterocyclicN-vinyl monomer to tat-olefin (4) of at least 2 carbon atoms orhalo-et-olefin is employed in t the simultaneous copolymerization andalkylation reacmfles i h fi gf 3 a 100 tion. When 0.02 to 0.1 mole oftit-olefin or halo-tz-olefin is Mm. (a) m 0188 of Nwinyl monomer chargedemployed per mole of heterocyclic N-vinyl monomer, mono-alkylationpredominantly takes place at random 1110163 Ill-Olefin charged X 0positions in the heterocyclic moiety of the copolymer yield- 1y1 re sultof Equatlon 3(b) 10 ing isomeric 1:1 adducts as illustrated above. Inother moles of N'vlnyl monomer charged words, the monoadducts (1:1) areisomeric with respect The copolymers obtained by the simultaneouscopolymto the position of the substitution (alkylation). For exerizationand alkylation reaction are characterized by the ample, with an N-vinylmoomer of a 5 6- or 7membered folowing formulae as determined from thesystematic h r y g y m m) r iz d by the quantitative study and from thestructural studies of for going g ne l f n an tit-olefin or fi numerousreaction products: random mono-alkylation takes place on the carbonatoms r norr-n R4-CH-A A-HC C=O A-H /C=O t t r T-CI-L CHzCH C-CIL CH2CH-L (CIIzCIIz)mR5 lp (CH2CHz)mR5 Jp R Rt--CII-A "R R4--CHA l I /0\ =0 /c=0l R1 *7 l C|CI{2' C1-lzCH- C-CH -CH2CH- L (C1I2CH2)mRs |p (CI'I2CH2)mR5lp wherein R and R have the same values as heretofore, R represents theatoms necessary to complete a 5-, 6- or 7- membered ring, R is eitherhydrogen or alkyl of from 1 to 180 carbon atoms, 2 is a numeral rangingfrom 10 to and wherein the ms independently represent a numerical valueof 0 to 1; when m is zero, R is hydrogen; when m is 1, R is eitherhydrogen or alkyl of about 1 to about carbon atoms, and wherein at leastone of the ms in at least one of the heterocyclic N-vinyl moieties hasthe value of 1.

From the foregoing formulae, it will be apparent to those skilled in thepolymer art that the value of p will depend primarily upon thereactivity ratios of the indi vidual heterocyclic N-vinyl monomers andthe tz-olefins or halott-olefins employed in the simultaneouscopolymerization and alkylation reaction.

The active sites on the N-heterocyclic monomer moieties in thecopolymers of the above formulae that are randomly alkylated(substituted by an alkyl group of from 2 to 180 carbon atoms) is bestillustrated with N-vinyl lactam moieties in such copolymers that arefree from lower alkyl substitutents designated by the values R and Rabove as follows:

(1120) TC II-alkyl alpha and omega to the carbonyl and on the tt-vinylcarbon atoms of the lactam moiety in said copolymer. Randommono-alkylation begins as the copolymerization reaction is initiated andcontinues after the copolymerization has been completed.

Where the N-vinyl monomer of a 5, 6- or 7-membered heterocyclic ringsystem employed in the reaction contains 1 or 2 alkyl groups of from 1to 2 carbon atoms in omega position to the carbonyl in the lactam moiety(as designated by the values R and R above), neglibible mono-alkylationtakes place in this position. In such case, the mono-alkylation takesplace primarily on the carbon atom alpha to the carbonyl and alpha vinylcarbon atom of the lactam moiety.

When 0.2 to 10 moles of Ot OlCfil']. of at least 2 carbon atoms areemployed per mole of N-vinyl monomer of a 5-, 6- or 7-memberedheterocyclic ring system, random mono-alkylation, di-alkylation,tri-alkylation, as well as polyalkylation take place at theaforementioned positions of the lactam moiety in the copolymer.

9 Di-alkylation and tri-alkylation are exemplified by the followingillustrations:

When 4 moles or more of an alpha-olefin or halo-a olefin are consumedper mole of monomeric N-vinyl lactam free from lower alkyl substitutentsas designated by the values R and R above, alkylated copolymeric N-vinyl lactams are obtained in which on the average one or more of thethree positions in the lactam moieties will contain a alkyl group of atleast 2 carbon atoms to as many carbon atoms as is contained in thealpha-olefin employed.

Since propagation occurs at a given alkylation site, i.e., one or moreadditional moles of a-olefin add to the first mole of a-olefin which hasadded to the lactam moiety, such propagation is termed polyalkylation asdistinguished from mono-, diand tri-alkylation. The tendency towardspolyalkylation (propagation) increases as the ratio of tot-olefin tolactam moiety increases and as the chain length of the u-olefindecreases. For example, when simultanelously copolymerizing andalkylating an N-vinyl lactam with ethylene, the molar ratio of thelatter propagated in the same positions as above described for theisomeric 1:1 adducts may range from 3:1, 4:1, 5:1 and 6:1. The 421 isexemplified by the following illustration:

With 1 mole of N-vinyl lactam and from 0.2 to 10 moles of l-butene,substitution at the above-described positions takes place to yield abutyl, or octyl or dodecyl group in the lactam moiety of the copolymer.

While the foregoing illustrations were directed to a monomer of N-vinyllactam, it is to be noted that the same mono-alkylation, di-, triandpolyalkylation take place on heterocyclic N-vinyl moieties over thanlactams. The non-lactam N-vinyl monomers, such as N-vinyl-Z-morpholinone, contains active protons in both 3 and 6 positions as wellas on the a-vinyl carbon atom, N-vinyl oxazolidone contains an activeproton in 5-position as well as on the u-vinyl carbon atom,N-vinyl-succinimide, N-vinyl diglycolylimide and N-vin'yl glutarimidecontain an active proton in alpha position to the carbonyl as well as onthe a-vinyl carbon atom. With such N-vinyl monomers alkylation takesplace at the active sites.

From the extensive studies and findings, it will be readily appreciated,depending upon the molar ratio of the reactants, that alkylatedcopolymeric Nvinyl lactarns and alkylated copolymers of otherheterocyclic N-vinyl monomers are obtained in which some or all of thecarbon atoms alpha and omega to the carbonyl and alpha-vinyl carbon atomof the lactam and of the heterocyclic N-vinyl moiety constituting thecopolymer contain at least one alkyl group of at least 2 carbon atoms.

The alkylated copolymers prepared in accordance with the presentinvention are new products which possess the varying degrees ofsolubility in polar and non-polar solvents, but insoluble in water, andwhich find many new and useful applications as will be notedhereinafter.

The new alkylated copolymers differ in solubility characteristics fromconventional polymeric N-vinyl lactams, i.e., (1) those prepared byhomopolymerizing N-vinyl lactams which do not contain from 1 to 2 alkylgroups of from 1 to 2 carbon atoms in the lactam moiety, and (2) thosewhich contain 1 to 2 of such alkyl groups in the lactam moiety, in thatthe latter two are soluble in water but insoluble in aliphatic andaromatic hydrocarbons, mineral oil, petroleum ether, ethyl ether, etc.,whereas the alkylated copolymers obtained in accordance with the presentinvention and containing at least one alkyl group of from 2 carbon atomsup in the N-vinyl lactam moiety are insoluble in water, but soluble inaliphatic and aromatic hydrocarbons such as n-hexane, n-heptane,benzene, toluene, kerosene, mineral oils, and in petroleum ether, ethylether, etc. The same applies to copolymers of the conventional N-vinyllactams and other monoethylenically unsaturated polymerizable monomers.For example, copolymers of mole percent of vinyl pyrrolidone and 35 molepercent of vinyl acetate and 60 mole percent of vinyl pyrrolidone and 40mole percent of methyl acrylate are partially soluble in water, butinsoluble in carbon tetrachloride, n-hexane and mineral oils.

The average molecular weights of the alkylated copolymers obtained inaccordance with the present invention vary from 5,000 (K10) to about50,000 (K40). The ease of solubility of the alkylated copolymers inaliphatic and aromatic hydrocarbons increases as the chain length of therat-olefin increases from 2 carbon atoms up.

It is interesting to note that by employing 1 mole of a specific N-vinyllactam such as, for example, N- vinyl-Z-pyrrolidone (VP) with varyingmolar ratios ranging from 0.11 to 1.8 mole of an ctr-olefin of from 4 to20 carbon atoms in the reaction, a variety of alkylated copolymershaving differing physical characteristics are obtained as may be notedfrom the following table:

TABLE 1.--l MOLE OF N-VINYL-2-PYRROLIDONE REACTED WITH- 1 mole 1.8 mole0A5 mole 0.11 mole 0.5 mole 0.22 mole Cam-olefin Cn-zoa-oletinCia-zoa-olefin Cream-Olefin Ora-olefin Ora-olefin Physical Form at 25 CWaxy solid Straw-colored Off-white solid. White granular Ofi-whi'tegranular White granular viscous liquid. solid. solid. solid. DensitygmJce. at 23 0....... 0.95 Average Mol. Weight 8, 600 Softening Point, C30 Melting range (Mannheim Block 0 32*36 83-90 146-152 131-140 1 3-195,

SOLUBILITY BASED ON 10% OF ALKYLATED COPOLYMER IN LISTED SOLVENTSWater." Ethanol. Toluene.

Mineral Oil Sol Tetraehloroethylene. ..l.. Sol

1 Dispersible denotes stable cloudy solution.

2 D.C. dispersihle cold.

The following examples will show how the various N- heteroeyclicmonomers are simultaneously copolymerized and alkylated. All parts givenare by weight unless otherwise noted.

For the sake of simplicity, the lubricating oil of paraffins stockhaving a Saybolt viscosity of 100 seconds marketed by the Socony MobilOil Company as 100 sec. solv. will be referred to hereinafter as 100sec. solvent.

It is to be noted that the isomeric distribution shown in the examplesis based on the findings of the systematic quantitative study.

EXAMPLE I Into a one-liter, four-necked flask, equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingingredients were charged:

N-vinyl-Z-pyrrolidone, 111 grams (1.0 mole) a-Eicosene, 140 grams (0.5mole) Methyl isobutyl carbinol, 200 grams Di-t-butyl peroxide, 11.0grams (0.075 mole) The flask was then purged with nitrogen and heated.When the temperature reached around 120 C. an exothermic reactioninitiated, but the temperature was controlled and maintained at 120-135C. After 16 hours of reaction, the experiment was discontinued and thecontents analyzed. The results showed the absence of any N-vinyl-2-pyrrolidone and 2.73% by weight of the solution of unreactedweicosene, corresponding to 91% consumption. The product after the totalremoval of the solvent and volatiles is a waxy solid at roomtemperature. It is soluble in alcohols and aliphatic and aromatichydrocarbons, but insoluble in water.

On the basis of Equation 1, the calculation showed that 86.45% of theweicosene charged was consumed in the copolymerization and alkylationreaction.

The minimum and maximum role percent of ot-eicosene copolymerized, ascalculated by Equations 2(a) and 2(b), are 2.0% and 20%, respectively.

The minimum and. maximum mole percent of a-cicosene consumed in thealkylation of the N-vinyl-2-pyrrolidone moieties, as calculated byEquations 3(a) and 3( b), are 66.45% and 84.45%, respectively.

The minimum and maximum mole percent of the N- vinyl-Z-pyrrolidonemoieties that were alkylated on the average, as calculated by Equations4(a) and 4(1)), are 33.22% and 42.22%, respectively.

The N-vinyl-2-pyrrolidone moieties in the copolymer that were alkylatedon the average showed the following isomeric distribution:

Position substitution: Percent Eicosyl in 3-position 70-80 Eicosyl in5-position l0-5 Eicosyl on wvinyl carbon atom -15 EXAMPLE 11 into aone-liter, four-necked flask equipped with stirrer, thermometer,nitrogen inlet and reflux condenser, the following ingredients werecharged and the flask then purged with nitrogen and heated:

N-vinyl-2-pyrrolidone:83.2 grams (0.75 mole) a-Dodecene l26 grams (0.75mole) Normal butanol:150 grams Di-tbutyl peroxide:l1 grams (0.075 mole)The contents of the flask were maintained at l20-125 C. for 12 hourswhen a second charge of peroxide (5.5 grams, 0.037 mole) was made andthe reaction continued for another 12 hours. (Total peroxide:16.5 grams,or 0.11 mole.) The solution was analyzed and found to contain noresidual N-vinyl-Z-pyrrolidone and only 2.26% by weight of the solutionof unreacted 0t-dOd6CCYl corre- Percent The mole percent of e-dodecenecopolymerized and alkylated 86.7 Min. mole percent of ot-dodecenecopolymerized 1.0

Min. mole percent of N-vinyl-Z-pyrrolidone moieties alkylated on theaverage 76.7

The N-vinyl-Z-pyrrolidone moieties in the copolymer that were alkylatedon the average showed the following isomeric distribution:

Position substitution: Percent Dodecyl in 3-position -85 Dodecyl in5-position 15-10 Dodecyl on u-vinyl carbon atom 10-5 EXAMPLE III Into aone-liter, four-necked flask equipped with stirrer, l thermometer,nitrogen inlet and reflux condenser, the following ingredients werecharged and the system purgedf wtih nitrogen: l

N-vinyl-2-pyrrolidone, 37 grams (0.33 mole) a-Dodecene, 336 grams (2.0mole) Normal butanol, 200 grams Di-t-butyl peroxide, 14.6 grams (0.1mole) The contents were brought to reflux (-125 C.) and; maintained for24 hours and then another 14.6 grams (0.1 mole) di-t-hutyl peroxide wasadded and heating continued for 24 more hours. (Total peroxide used=29.2grams or 0.2 mole.) The contents were then cooled and analyzed. It wasfound to contain no residual N-vinyl-Z pyrrolidone and only 4.65% byweight of solution of unreacted a-dodecene, corresponding to 91.7% ofu-dodecene consumed in the reaction. The product obtained after theremoval of all the volatiles in high vacuum, is colorless and viscousfluid soluble in all organic polar and non-polar solvents, but insolublein water.

EXAMPLE 1V Into a one-liter stainless steel shaker bomb, a preparedsolution of 111 grams (1.0 mole) N-vinyl-2-pyrrolidone, 200 gramsethanol and 25' grams (0.17 mole) di-t-butyl peroxide was charged andthen the bomb capped and 140 grams of ethylene injected and the bombsealed. The bomb Was heated and maintained at C. with shaking for 24hours. It was then cooled, vented and the contents discharged into astainless steel pan and placed in vacuum oven. After a continuous dryingperiod of two days at 90 C. (20-30 mm. of mercury) the dried product Wasanalyzed and found to contain no N-vinyl pyrrolidone but 6.8% nitrogen,corresponding to 46% by weight of grafted ethylene in the finalcopolymerized and alkylated product. The product is a light browntransparent semi-solid soluble in polar and nonpolar organic solvents,but insoluble in water.

EXAMPLE V into a one-liter, four-necked flask equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingingredients were charged and the system then purged with nitrogen:

N-vinyl-2-pyrrolidone=lll grams (1.0 mole) u-Eicosene 280 grams (1.0mole) Methyl isobutyl carbinol:200 grams Di-t-butyl peroxide=l4.6 grams(0.1 mole) The contents were maintained at 130-135 C. for 16 hours andthen a second addition of 7.3 grams (0.05 mole) peroxide was made andreaction continued for 8 more hours. (Total peroxide=2l.9 grams, 0.15mole.) The solution was cooled and analyzed. The analytical data showedthe total absence of N-vinyl-Z-pyrrolidone and only 5.48% by weight ofsolution of unreacted w eicosene, corresponding to 88% of a-eicoseneconsumed in the reaction. The contents were subjected to vacuumdistillation and as the solvent and volatiles were removed, 391 g. 100sec. solv. were added. At completion, a clear viscous fluid weighing 780grams was obtained. On cooling to room temperature the productconcentrate turned to a waxy solid, but became a clear fluid on warming.

EXAMPLE VI Into a one-liter, four-necked flask equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingmaterials were charged:

N-vinyl-2-piperidone=125 grams (1.0 mole) a-Octadecene=252 grams (1.0mole) Normal butanol=200 grams Di-t-butyl peroxide=1-4.6 grams (0.1mole) Percent The mole percent of a-octadecene copolymerized andalkylated 88.26 Min. mole percent of a-octadecene copolymerized 1.0 Min.mole percent of N-vinyl-Z-piperidone moieties alkylated on the average78.26

The N-vinyl-Z-piperidone moieties in the copolymer that were alkylatedon the average showed the following isomeric distribution:

Position substitution: Percent Octadecyl in 3-position 60-70 Octadecylin 6-position 25-20 Octadecyl in a-vinyl carbon atom -10 EXAMPLE VIIInto a one-liter, four-necked reaction flask, equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingmaterials were charged:

N-vinyl-e-caprolactam=139 grams (1.0 mole) a-Octadecene=2l4 grams (0.85mole) Methyl isobutylcarbinol=200 grams Di-t-butyl peroxide=18.5 grams(0.127 mole) The flask was then purged thoroughly with nitrogen, heatedand maintained at 125-135 C. for 24 hours. The contents when analyzedshowed the absence of N-VillYI-ecaprolactam and the presence of 4.54% byWeight of the solution of unreacted a-octadecene, corresponding to 81.5%of ot-octadecene consumed in the reaction. After stripping the solventand volatiles in vacuum, the product obtained is a very viscous fluidsoluble in all non-polar solvents.

Percent The mole of a-octadecene copolymerized and alkylated 77.43 Min.mole percent of a-octadecene copolymerized 1.17 Min. mole percent ofN-vinyl-e-caprolactam moieties alkylated on the average 55.8

The Nvinyl-eca.prolactam moieties in the copolymer that were alkylatedon the average showed the following isomeric distribution:

Position substitution: Percent Octadecyl in 3-position 50-60 Octadecylin 7-position 30-25 Octadecyl on u-vinyl carbon atom 20-15 EXAMPLE VIIIInto a one-liter, four-necked flask equipped with stirrer, thermometer,nitrogen inlet and reflux condenser, after a thorough nitrogen purge,the following ingredients were charged and heated:

N-vinyl-5-methyl-2-pyrrolidone:125 grams 1.0 mole) Hexanol (mixture ofisomeric hexanols) :200 grams a-Octadecene 227 grams (0.9 mole)Di-t-butyl peroxide=15 grams (0.1 mole) The solution was maintained .at120-140 C. for 30 hours and then cooled and analyzed. It was found tocontain less than 0.1% by weight of monomer and only 6.0% by weight ofsolution of unreacted a-octadecene, corresponding to consumption in thereaction. After stripping the organic solvent and volatiles in vacuum,the product is a very viscous fluid at room temperature. It is solublein all non-polar solvents, but insoluble in water.

Percent The mole percent of u-octadecene copolymerized and alkylated80.75 Min. mole percent of a-octadecene copolymerized- 1.11 Min. molepercent of N-vinyl-5-methyl pyrrolidone moieties alkylated on theaverage 62.6

The N-vinyl-S-methyl pyrrolidone moieties in the copolymer that werealkylated on the average showed the following isomeric distribution:

Position substitution: Percent Octadecyl in 3-position 80-90 Octadecylin 5-position Negligible Octadecyl on d vil'lyl carbon atom 20-10EXAMPLE IX Into a one-liter, four-necked flask equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, after a thoroughnitrogen purge, the following ingredients were charged:

N-vinyl-2-oxazolidone=56.5 grams (0.5 mole) Methyl isobutylcarbinol=200grams a-Eicosene=210 grams (0.75 mole) Di-t-butyl peroxide=11.0 lgrams(0.075 mole) The mixture was then heated and maintained at -140 C. for12 hours and the another 11.0 grams (total peroxide=22.0 grams, 0.15mole) peroxide added and the reaction continued. After a total of 28hours reaction period, the contents were cooled and analyzed. It wasfound to contain 0.1% by weight of solution of residual N-vinyloxazolidone and 3.44% of unreacted ot-eicosene, corresponding to 92%consumption of the a-eicosene. The product, after stripping the solventand volatiles in vac uum, is a viscous fluid while hot, solidifying uponcooling to room temperature to a waxy solid. It is soluble in aliphaticand aromatic hydrocarbons, but insoluble in water.

EXAMPLE X Into a one-liter, four-necked flask equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingingredients were charged:

N-vinyl-S-morpholinone=63.5 grams (0.5 mole) Normal butanol=150 gramsa-Hexadecene=224 grams (1.0 mole) Di-t-butyl peroxide=l grams (0.1 mole)Into a one-liter, four-necked flask equipped with stirrer, thermometer,nitrogen inlet and reflux condenser, the following ingredients werecharged:

N-vinyl succinimide=62.5 grams (0.5 mole) Methyl isobutylcarbinol=l50grams a-Eicosene=182 grams (0.65 mole) *Di-t-butyl peroxide= grams (0.1mole) The flask was purged with nitrogen, heated and maintained at arange of 120-140 C. for hours. The contents were then cooled andanalyzed and found to contain only a trace of N-vinyl succinimide and3.66% by weight of solution of unreacted a-eicosene, corresponding to91.8% consumption of a-eicosene in the reaction. After stripping thesolvent and volatiles in vacuum, the product is a viscous fluid whilehot, solidifying upon cooling to room temperature to a waxy solid. it issoluble in all non-polar solvents, but insoluble in water.

Percent The mole percent of a-eicosene copolymerized and alkylated 87.21Min. mole percent of ot-eicosene copolymerized 0.77

Min. mole percent of Nwinyl succinimide moieties alkylated on theaverage The N-vinyl succinimide moieties in the copolymer that werealkylated on the average showed 80-90% eicosyl substitution in the3-position (in both of the alpha to carbonyl carbon atoms) and 10-20%eicosyl substitution on the a-vinyl carbon atom.

EXAMPLE XII N-vinyl-Z-pyrrolidone (111 grams, 1 mole) were dissolved in250 grams of anhydrous ethanol and then 146 grams (0.1 mole) ofdit-butyl peroxide added and the solution transferred into a one-literstainless steel rocker bomb. Chlorotrifluoroethylene (CClF-:CF 60.0grams (0.51 mole) was then charged to the bomb and the bomb heated andmaintained at 125-130 C. for 24 hours. After cooling, the contents weredischarged into a oneliter, four-necked flask and subjected to vacuumdistillation to remove solvent and light boiling components. The drysolid obtained as residue analyzed for 13.3% of fluorine and 7.7% ofchlorine corresponding to 27% of the chlorotritluoroethane by weight ofthe product.

EXAMPLE XIII Into a oneliter, four-necked flask equipped with stirrer,

thermometer, nitrogen inlet and reflux condenser, the followingmaterials were charged:

N-vinyl-2-pyrrolidone 111.0 grams (1.0 mole) u-Octene 112.21 grams (1.0mole) Normal butanol 200 grams Di-t-butyl peroxide 14.6 grams (0.1 mole)The flask was purged thoroughly with nitrogen and heated. The contentswere maintained at reflux for 30 hours and then cooled and analyzed. Theanalysis showed the total absence of N-vinyl-Z-pyrrolidone and thepresence of only 3% by weight of solution of u'nreacted a-octene,corresponding to 88.1% consumption of the tat-olefin.

After stripping in vacuum the solvent and volatiles, the product is aflexible solid, soluble in petroleum ether, mineral oils, toluene,benzene, and polar solvents, but insoluble in water.

EXAMPLE XIV Into a one-liter, four-necked flask equipped with stirrer,thermometer, nitrogen inlet and reflux condenser, the followingmaterials were charged:

N-vinyl-2-pyrrolidone 55.5 grams (0.5 mole) C u-olefin obtained by thetrimerization of oc-tetradecene 294 grams (0.5 mole) Methylisobutylcarbinol grams Di-tbutyl peroxide 15 grams (0.1 mole) The flaskwas purged thoroughly with nitrogen and heated. The contents weremaintained at reflux for 24 hours and then cooled and analyzed. Theanalysis showed the total absence of N-vinyl-Z-pyrrolidone and only7.75% by weight of the solution of unreacted C ll-olefil'l,corresponding to 87.2% consumption of the rx-olefin.

When all solvent and volatiles were stripped in vacuum, an amber coloredwax was obtained which is soluble in mineral oil and other non-polarsolvents.

From the foregoing specification and illustrative work- L ing examples,it becomes clearly evident that by the simultaneous copolymerization andalkylation process of. the present invention, the solubility of thealkylated co polymers is systematically controlled, both by the type' ofa-olefin used and the amount thereof, so that cOpOlymers which are stillsoluble in polar solvents such as alcohols to copolymers which aresoluble in aliphatic hydrocarbons, mineral and lubricating oils can beobtained as well as copolymers having intermediate degrees of solubilitybetween polar and non-polar solvents. Thus, copolymers with a low degreeof alkyation can be obtained which are still soluble in ethanol so thatthey can be formulated with Freons as aerosol hair sprays, but theirsensitivity to moisture is reduced. For example, heterocyclic N-vinylmonomers which are copolymerized and alkylated with ethylene, propyleneor l-butene to the extent of 15% to 30% flt'olefill'l by weight yieldcopolymers that are soluble in anhydrous ethanol and can be formulatedwith Freons as aerosol hair sprays having increased moisture resistance;In other words, the simultaneous copolymerization and alkylation of suchmonomers with a-olefins of from 2 to 4 carbon atoms to the specifieddegree of alkylation yield copolymers which are more flexible and lesstacky under high humidity conditions than conventional homopolymers ofN- vinyl pyrrolidone or N-vinyl pyrrolidone/vinyl acetate copolymers.The flexibility of the alkylated copolymers increases and the tack athigh humidity decreases as the degree of alkylation increases. Thesecopolymers can also be formulated into adhesives with superiorproperties because of their increased resistance to moisture.

Polymers with a high degree of alkylation are soluble in lubricatingoils and are useful as sludge dispersants and viscosity index improvers.The latter polymers are also soluble in hydrocarbon polymers such aspolyethylene and impart dye receptivity to these diflicultly dyedpolymers.

The alkylated copolymers, including those obtained by copolymerizationand alkylation of hcterocyclic N-vinyl monomers with loweralpha-olefins, are compatible at all levels with epoxy resins,polystyrene, polyvinyl acetate, and with copolymers of vinyl chlorideand vinyl acetate.

The heterocyclic N-vinyl monomers when simultaneously copolymerized andalkylated with a-olefins of from 8 to 42 carbon atoms yield lube-oiladditives which not only improve the viscosity index of lubricatingoils, but also impart thereto excellent sludge and corrosion inhibitingproperties. Of particular utility in this regard are the alkylatedcopolymers prepared by the simultaneous copolymerization and alkylationof 0.5 equivalent of N- vinylpynrolidone with 0.35 mol of e-eicosene,one equivalent of N-vinylpiperidone with one mole of n-dodccenc, and0.25 equivalent of N-vinyl-a-caprolactam with 0.3 mole of a-hexadecene.

The alkylated copolymers in which at least 25 mole percent of theheteroeyclic N-vinyl moieties in the copolymer are alkylated on theaverage by at least one alkyl substituent of from 10 to 42 carbon atoms,display emollient properties, i.e., softening and soothing effect whenapplied to the skin and the appendages of the skin. in view of thischaracteristic, they are excellent additives to soaps and cosmeticpreparations of the clcansing, conditioning and embellishing type whichwill impart a smooth texture as well as a softening and soothing effectto the skin and skin appendages. The alkylated copolymers can be used inplace of, and in addition to, petroleum hydrocarbons, i.e., mineraloils, petrolatums and paraffin waxes. They are not only soluble in thesepetroleum hydrocarbons, but also soluble in other unctuous materialssuch as fatty acids; stearic, myristic oleic acids, etc.; glycerylmonostearate (Glycosterin); lanolin (wool fat); beeswax and other animaland vegetable waxes; higher alohols, such as hexanol, myristyl alcohol,etc.; polyoxyalkylene glycols, e.g., polyoxyethylene glycol,polyoxypropylene glycol; methyl ethyl ketone, Cellosolve, butyrolactone,etc., which are employed in toiletry preparations of this type. They arereadily emulsified by the usual reagents employed in toiletrymanufacture. By virtue of this solubility, enmlsifiability and broadcompatibility with other components of the toiletry preparation, theysubstantially reduce or eliminate the drying tendency of mineral oilsand petrolatums present in such preparations. The presence of theadditive (alkylated copolymer) in toiletry preparations containingparaffin wax eliminates the clogging of pores. Regardless whether thetoilctry prepara tion contains any one or all of these petroleum hydrocarbons, vegetable oils, lanolin, and/or other unctuous components, oris free from such components, etc., the presence of the additive in suchpreparation imparts a much smoother texture to it with the attendantsoftening and soothing edect when spplied to the skin and s softeningeffect when applied to skin appendages.

The amount of elkylated copolymer that is employed to effect the desiredresults (smoother texture with softening and soothing effects) rangesfrom about 0.1% to about 0% by weight based on the total weight of thecompleted oiletry preparation. The alkylsted copolymers are added at anystage of manufacture of cold creams, cleansing creams, emollient creams,finishing creams, skin'softcning lotions, hand cleaners, lubricatingcreams, overnight creams, absorption-base creams, hand creams andlotions, foot creams, baby creams, baby skin oils; special creams, suchas astringent creams, bleaching creams, acne creams: protective creams(industrial creams), lotion or aerosol skin protective coatings, aerosolbandage sprays, vanishing creams, foundation creams, brushless shavingcreams, shaving preparations. sfteMhave lotions and sprays, medicatedcreams, deodorant: and snti-perspirsnts, such as deodorant creams andlotions, roll-on deodorsnts, sunburn preventlves, suntan preparations,paste or lotion rouges, cream rouges, massage oils, facial masks,depilatories, le., hair removers (epilating was compositions) and hairremoving creams, paste or lotion face makeup, face powders; eye makeup,i.e., eye shadows and eyebrow creams;

fingernail creams and cleaners, hair bleaches and tints, cuticlesofteners, hair conditioners, wave sets, hair dressings, hairbrilliantines; hair oils, hair sprays, creams and shampoos, nail polishremovers, lipsticks, perfume sticks, facial soaps, synthetic soap bars,antiseptic soaps (tincture of green soap), insect repellents, protectivehand creams, waterless hand cleaners, dentifrice, pet shampoos, bathtales, and the like. They are helpful in stabilizing aqueous foams intoiletry preparations such as soap bars, shaving creams, etc.

Toiletry preparations containing the alkylated copolymcr render thepreparation smoother in texture and easier in application to the skinand its appendages (hair and nails). After application to the skin orscalp, the preparations leave the skin soft and pliable with a soothingeffect which remains after the preparation is removed by washing withsoap and water. After application to the hair, the preparation depositsa film which renders the hair smooth, soft, lustrous and alive-looking.The soft and smooth effects remain after washing with soap and water andenhance the manageability of the hair. After ap lication of the nailpreparations, the nails are smooth and the adjacent skin rendered softand pliable with a soothing effect. The alkylated copolymers areeffective pigment dispersers and act as color receptors in rouges andlipsticks.

In hair preparations the presence of the alkylated copolymer improvesthe softness, water repellency and manageability of the hair. In hairconditioners, the alkylated copolymers may be added to creams, foams orgels and the resulting preparations pressurized with nitrogen, argon, orthe usual liquefied fiuorochloro-hydrocarbons.

in view of their solubility in hydrocarbons, mineral oils, etc., thealkylated copolymers are particularly adaptable for use as hot meltsalone or in combination with paraffin waxes as coatings for variousfibrous materials. Extruded films from such alkylated copolymers, eitheralone or with waxes and resins, may be composited to paper and otherfibrous or textile materials. The alkylated copolymers are compatiblewith a wide variety of resins, waxes, and polymers at room or elevatedtemperatures. They are useful as binders and saturants in hard board andparticle board.

Copolymers, in which at least: 60% of the heterocyclic N-vinyl moietiesalkylated on the average by an alkyl group of from l8 to 42 carbonatoms, are useful for the protection of wires and cables in the form ofouter jackets and sheets. Films or coatings of such alkylated copolymersare also useful as liners for metal or fiber drums for shipping moist,dusty or corrosive product. They are also useful in electrical equipmentsuch as in electric cable insulation, in potting dopes for capacitorelements, and as insulsting coatings, sealing compounds, and inmoistureproofing coils, resistors and paper capacitors; as caulkingcompounds, spreader-sticker for insecticidal compositions,water-proofing sealants, adhesives, water-proofing, gum and resinplasticizers, paper coatings, metal rolling and as dispersants for inksand dye pastes. They are useful in leather treatment as dye assistants,dye stripping agents, textile water-proofing, textile warp size, and thelike.

Emulsions of the alkylated copolymers are especially useful in theimpregnation of paper. When mixed in amounts ranging from about 1 to 3%by weight in light mineral oils, the alkylated copolymers functioneffectively gsolpenetrants in the removal of rusty and frozen nuts andThe alkylated copolymers are especially adaptable in dye stripping, aspigment dispersants and protective colloids, temporary protectivecoatings, coatings for paper, binders for detergent briquettes and asbinders for tablets and as color dispersant! in tablet coating. Films ofthe alkylated copolymers, from aqueous dispersion or emulsion, areeffective for spraying various plants so as to protect them duringtransplanting or prevent rapid transpiration during sunny and relativelywarm winter months.

The alkylated copolymers are useful in dispersing l9 gums, resins andvarious types of polymers. They are particularly adaptable inlubricating oils as sludge disperscrs, and as bonding agents for paper,plastics and textile fabrics. They are very useful as anti-redepositionagents in detergents, as detergent hydrotropes and/or pacifiers, in drycleaning detergents, foam stabilizers for shampoos, stabilizers for highdensity and low density liquid detergents, foam stabilizers for mistdrilling of oil or gas wells, latex stabilizers, hydraulic fluidemulsion stabilizers, suspending agents and protective colloids forpolymer emulsions and in emulsion polymerization reactions, inhibitorsfor clay hydration slushing, oil corrosion inhibitors, engine oil rustinhibitors, complexing agents for liquid-liquid extraction, dyereceptors for polypropylene, dye fixing agents, pigment dispersants andprotective colloids in pigment printing, fiuidizing agents for papercoating slurries, pitch dispersant; adhesives in place of starch,casein, synthetic latices and the like; antistatic agents forpolystyrene, polyethylene, polypropylene and other plastics, tackifiersfor polyolefins and other plastics, fiexibilizing agents for phenolicand other therrno setting resins, dispersants and gloss irnprovers infioor wax polishes, thickening agents in non-aqueous systems, asmembranes for desalting and filtration, as adhesion pro motors forpaperboard to nylon and as dye receptors for Creslan. They are useful asadditives to natural and synthetic waxes to lower melt viscosity,improve dispersibility, flexibility, gloss, or hardness. They are usefulas ink acceptors for surface printing of high density polyethylenebottles, abeorbents for tobacco tars in cigarette filters, absorbentsfor toxic gases and vapors; complexing agents for dyestuffs, phenoliccompounds and heavy metal ions; thickeners for petroleum oilsand oilbase paints; fiocculating agents in sewage treatments, as coating foradhesive tapes and as components in adhesive hot melts, melting pointdepressants for natural and synthetic resins, as reinforcing agents forglues and as reducers of the hydrophilic character of polar resins.

The alkylated copolymers are excellent dye receptors for polyolefinfibers such as polyethylene, polypropylene and polybutene. They are alsoexcellent for sizing polypropylene filament and spun yarns in view oftheir good adhesive properties on polypropylene surfaces. They addstrength and good dyeing properties when employed with rayon, bothviscose and acetate. They are excellent sizers for glass fibers sincethey have the adhesion due to the N-vinyl lactam units but betterlubricity because of the alkyl units. The alkylated copolymers improvethe gloss of waxes and polishes. they are better soil suspending agentsthan the corresponding unalltylated polymers in synthetic detergents.They are especially useful in the deemulsification of crude oilemulsions. They are useful as soil dispersing agents for syntheticfibers. In the textile industry, they are useful as adhesives,anti-static agents, lubricants, dye assistants, dye leveling agents andas filament spinning finishes. They are also useful as tacltifiers.plasticizers, fiocculators of ore fines, etc., as gelling agents and asbeverage clsrifiers.

The alltylated copolymers display dispersing and detergent propertieswhen incorporated into petroleum products et a concentration of about0.03% to by weight, such as kerosene, fuel oils, jet fuels and othercombustible hydrocarbon liquids. They readily disperse gums, resins(asphaltenes) in such products.

The alkylated copolymers are also useful as mold release lubricants, asanti-tack and anti-block agents, as lubricants and anti-static agentsfor films and textile fibers, and as flattening, softening and sizingagents for textiles. 'lhey are compatible with petroleum resins and themixture employed in water-proofing, pipe coating compounds, and asconcrete curing compounds to insure the deposition of a water-proofmembrane. In carbon paper, the alkylated copolymers serve as a vehiclefor carrying the color and prevent the ink from soaking completely intothe paper. Polyethylene containing sodium 20 bicarbonate and thealkylated polymers in which the lactam units contain alkyl groups offrom 6 to 10 carbon atoms can be extruded coaxially with a core to givea foam-sheathed cable. They are especially useful as cell control agentsin polyurethane foam.

The alkylated copolymers form halogen adducts with elemental iodine,iodine monochloride and iodine monobromide. The iodine adducts areprepared by gently heating the alkylated copolymer until it melts andwith con-, stant stirring adding elemental iodine or a solution of elc"mental iodine in alcohol or carbon tetrachloride or a mixturc thereof.From 1 to 12% of iodine by weight of alkylated copolymer may beincorporated to the molten copolymer. The resulting iodine adduct issoluble in a pharmaceutical grade mineral oil and other unctuousmaterials. The iodine adduct may be incorporated in powders, ointments,salves, suppositories, and toiletry preparations (cosmetics and soaps)to yield antiseptic and germicidal compositions which impart a soft,smooth and softening effect to the skin.

The alkylated copolymers are useful additives to automobile polishes toincrease gloss and as rust inhibitors in priming and finishing paintsfor metals. The alkylated polymers are readily chlorinated byconventional procedures to yield a new and useful class of polymershaving fire-retarding properties.

The alkylated copolymers when incorporated into nonanionic and anionicsurfactants in amounts ranging from about 3 to 5% by weight of thesurfactant, counteract the defatting tendencies and the accompanyingchapping appearance when in contact with human skin, by leaving the skinsoft and pliable with a soothing effect, which remains after severalrinsings of water.

While the present specification has shown the simultaneouscopolymerization and alkylation of a large class of heterocyclie N-vinylmonomers, N-vinyl lactams other than those illustrated above may beemployed in the copolymerization and alkylation with an a-oiefin orhaloe-olefin of at least two carbon atoms. Such monomers include N-vinylalkyl-substituted derivatives of lactams, for example,4,4-dimethyl-2-pyrrolidone; 3,3-dimenthyl-2- pyrrolidone;3-ethyl-2-pyrrolidone; 3,5-dimethyl-Lpyrrolidone; S-methyl-Lpyrrolidone;4-methyl-2-pyrrolidone, 3,3,S-trimethyl-Lpyrrolidone;5,6-dimethyl-2-piperidone; 4-ethyl-2-piperidone;S-methyl-6'ethyl-2-piperidone; 3- methyl 2 piperidone; 4methyLZ-piperidone; 3,6-dimethyl-2-caprolactam; 4.6dimethyl-Z-caprolactam; 4.7 dimethyl-Z-caprolactam;3-ethyl-2-caprolactam; S-ethyl- Z-caprolactam; 6-ethyl-2caprolactam;4-ethyl-6-methyl-2- caprolactam; 6-methyl-2-caprolactamr;4-methyl-6ethyl-2- caprolactam; 3-methyl-2-caprolactam;4-methyl-2-eaprolactam; and G-methyI-Z-caprolactam. Despite the factthat some of these monomers contain an ailtyl group in either alphaand/or omega positions to the carbonyl, any one of the latter twopositions free from such alkyl substitu ents as well as the alpha-vinylcarbon atom will nevertheless be copolymerized and alkylated to yieldcopolyme containing at least one additional aikyl substituent of itleast 2 carbon atoms in the lactam moieties of sai copolymers.

The copolymeric haloalkylates of heterocycllc N-vinyl monomers andhalo-a-olefiins of at least 2 carbon atoms are also a new and usefulclass of products having fireretardant properties. They are especiallyuseful in the formulation of fire-retardant adhesives, i.e., bondingagents for paper, plastics and textile fabrics. From solutions in avariety of organic solvents or as emulsions, the haloalkylatedcopolymers form smooth continuous films which make them particularlyuseful as fire-retardant precoating agents for polyester laminates.

We claim:

1. Alkylated linear copolymer of 5- to 7-membered heterocyclic N-vinylmonomer and a-Oicfil'l comprising recurring structural units selectedfrom the clause consisting of those having the following formulae:

wherein R and R are selected from the class consisting of hydrogen,methyl and ethyl, R is selected from the class consisting of hydrogenand alkyl of from 1 to about 180 carbon atoms, R is a member selectedfrom the class consisting of an oxy and methylene group, R is selectedfrom the class consisting of methyl and ethyl, n is an integer of from 1to 3 and p is an integer of from 10 to 100, and wherein the msindependently represent a numerical value of 0 to 1; when m is zero, Ris hydrogen; 75 when m is 1, R is selected from the group consisting ofwith 0.05 to 10 moles of an wolefin of from 2 to about 180 carbon atomsin solution of an organic solvent common to the said heterocyclicN-vinyl monomer and u-olefin in the presence of 0.025 to 0.30 mole of anorganic peroxide catalyst per mole of said a-olefin at a temperatureranging from 80 to 200 C.

10. The process of simultaneously copolymerizing and alkylating anNvinyl lactam with an a-olefin which commo)n oH-(omoH9-R5 (HrC)n CH(among-11. l

wherein R is selected from the group consisting of hydrogen and alkyl,of from 1 to about 180 carbon atoms, n is an integer of from 1 to 3 andP is an integer of from 10 to 100, and wherein the ms independentlyrepresent a nu merieal value of to 1; when m is zero, R is hydrogen;when m is 1, R is selected from the group consisting of hydrogen andalkyl of from 1 to about 180 carbon atoms, and wherein at least one ofthe ms in at least one of the N-vinyl lactam moieties has the value of1, said alkylated copolymer having a molecular Weight of at least 5,000.

3. Alkylated copolymer of N-vinyl lactam and (It-Olefin comprisingrecurring structural units having the following prises heating one moleof an N-vinyl lactam with 0.05 to moles of an a-olefin of from 2 toabout 180 carbon atoms in solution of an organic solvent common to thevinyl lactam is N-vinyl2-piperidone.

14. The process according to claim 10 wherein the N- vinyl lactam isN-vinyl-e-caprolactam.

15. The process according to claim 9 wherein the 5- memberedheterocyclic N-vinyl monomer is N-vinyl succinimide.

16. The process of simultaneously copolymerizing and alkylatingN-vihyl-Z-pyrrolidone with u-CiCOSCIle which comprises heating one moleof said p yrrolidone with 0.5 mole of a-eicosene in solution of methylisobutylcarbinol in the presence of 0.075 mole of di-t-butyl peroxide ata temperature of l20135 C.

17. The process of simultaneously copolymerizing and alkylatingN-vinyl-5-methyl-2 pyrrolidone which comprises heating one mole of saidpyrrolidone with 0.9 mole of a-oetadecene in solution of hexanol in thepresence of 0.1 mole of di-t-butyl peroxide at a temperature of l20l40C.

18. The process of simultaneously copolymerizing and alkylating N-vinylsuccinimide which comprises heating one mole of said succinimide with1.3 moles of u-eicosene in solution of methyl isobutylcarbinol in thepresence of 0.2 mole of di-t-butyl peroxide at a temperature of C.

19. The process of simultaneously copolymerizing and alkylatingN-vinyl-2-piperidone which comprises heating one mole of said piperidonewith 1 mole of u-octadecene in solution of nbutanol in the presence of0.1 mole of dit-butyl eroxide at a temperature of 120 C.

wherein R and R are selected from the group consisting of hydrogen,methyl and ethyl, R is selected from the group consisting of hydrogenand alkyl, of from 1 to about carbon atoms, n is an integer of from 1 to3 and p is an integer of from 10 to 100, and wherein the msindependently represent a numerical value of 0 to 1; when In is Zero, Ris hydrogen; when m is 1, R is selected from the group consisting ofhydrogen and alkyl of from 1 to about 180 carbon atoms, and wherein atleast one of the ms in at least one of the N-vinyl lactam moieties hasthe value of 1, said alltylated copolymer having a molecular weight ofat least 5,000.

4. Alkylated copolymer according to claim 2 wherein the N-vinyl lactamis N-vinyl-2-pyrrolidone.

5. Alkylated copolymer according to claim 3 wherein the N-vinyl lactomis N-vinyl-S-methyl-2-pyrrolidone.

6. Alkylated copolymer according to claim 2 wherein the N-vinyl lactamis N-vinyl-Z-piperidone. J5

7. Alkylated copolymer according to claim 2 wherein the N-vinyl lactamis N-vinyl-e-caprolactam.

8. Alkylated copolymer according to claim 1 wherein the S-memberedheterocyclic N-vinyl monomer is N-vinyl succinimide.

9. The process of simultaneously copolymerizing and alkylating 5- to7-membered heterocyclic N-vinyl monomers having a carbonyl functionadjacent to the nitrogen in its heterocyclic moiety with a-olefins whichcomprises heating one mole of said heterocyclic N-vinyl monomer saidN-vinyl lactam and a-olefin in the presence of 0.025

13. The process according to claim 10 wherein the N- 20. The process ofsimultaneously copolymerizing and alkylating N-vinyl-e-caprolactam whichcomprises heating one mole of said caprolactam with 0.85 mole oftx-OCtadecene in solution of methyl isobutylcarbinol in the presence of0.127 mole of di-t-butyl peroxide at a tempera ture of 125 to 135 C.

21. Alkylated copolymer according to claim 2 wherein R is alkyl of from2 to 40 carbon atoms.

22. Alkylated linear copolymer of 5- to 7-membered heterocyclic N vinylmonomer having a carbonyl function adjacent to the nitrogen in itsheterocyclic moiety, comprising recurring structural units having thefollowing formula:

R is selected from the group consisting of hydrogen and alkyl of from 1to about 180 carbon atoms and p is an integer of from 10 to 100, andwherein the ms independently represent a numerical value of 0 to 1; whenm is 0, R is hydrogen; when m is 1, R is selected from the groupconsisting of hydrogen and alkyl of from 1 to about 180 carbon atoms,and wherein at least one of the ms in at least one of the heterocyclicN-vinyl moieties has the value of 1 .in at least one of the positionsselected from the group consisting of alpha and omega carbon atoms tothe said carbonyl and alpha-vinyl carbon atom in said moieties, saidalkylated copolymer having a molecular weight of at least 5,000.

ut on -otn R5 it, (onions-n5 j". /m nt oniorrgo=0 R5--/CHZCII2 tc=o ml tt t T-on. onion o-on tr-ion L (among-13, L (linens-R5 j /m p /m pwherein R represents the radical necessary to complete a 5- to7-membered heterocyclic ring system selected from the class consistingof R R1 wherein R and R1 are selected from the group consisting of -C111-, 0 hydrogen, methyl and ethyl References Cited JOSEPH L. SCHOFER,Primary Examiner.

HARRY WONG, ]R., Assistant Examiner.

U.S. Cl. X.R.

1. ALKYLATED LINEAR COPOLYMER OF 5- TO 7-MEMBERED HETEROCYCLIC N-VINYLMONOMER AND A-OLEFIN COMPRISING RECURRING STRUCTURAL UNITS SELECTED FROMTHE CLAUSE CONSISTING OF THOSE HAVING THE FOLLOWING FORMULAE:
 10. THEPROCESS OF SIMULTANEOUSLY COPOLYMERIZING AND ALKYLATING AN N-VINYLLACTAM WITH AN A-OLEFIN WHICH COMPRISES HEATING ONE MOLE OF AN N-VINYLLACTAM WITH 0.05 TO 10 MOLES OF AN A-OLEFIN OF FROM 2 TO ABOUT 180CARBON ATOMS IN SOLUTION OF AN ORGANIC SOLVENT COMMON TO THE SAIDN-VINYL LACTAM AND A-OLEFIN IN THE PRESENCE OF 0.025 TO 0.30 MOLE OF ANORGANIC PEROXIDE CATALYST PER MOLE OF SAID A-OLEFIN AT A TEMPERATURERANGING FROM 80* TO 200*C.